Zr改性Ni2P/SBA-15催化剂的制备及其加氢脱氧性能

以正丙醇锆（n）和Zr（SO₄）₂（m）为锆源制备了Zr改性的Ni₂P/ZrO₂-SBA-15（n）和Ni₂P/ZrO₂-SBA-15（m）催化剂，并采用XRD、BET、CO吸附、XPS、NH₃程序升温脱附等手段对催化剂进行了表征。以苯并呋喃（BF）为模型化合物，研究了催化剂加氢脱氧（HDO）性能。结果表明，Zr改性后，形成了新的层状结构的ZrP；Zr的引入有助于生成更多、更小粒径的Ni₂P活性相，催化剂的酸强度和酸量均提高。与正丙醇锆相比，Zr（SO₄）₂为锆源能够获得比表面积大、酸性强、酸量大的催化剂，得到更多的ZrP相、更小粒径的Ni₂P晶粒，暴露更多的Ni活性位点。Ni₂P/ZrO₂-SBA-15（n）和Ni₂P/ZrO₂-SBA-15（m）的BF HDO产率分别为71.5%和85.9%，较Ni₂P/SBA-15分别提高了14.0%和28.4%。催化剂HDO活性、脱氧产物选择性和产率大小顺序为：Ni₂P/ZrO₂-SBA-15（m） > Ni₂P/ZrO₂-SBA-15（n） > Ni₂P/SBA-15。

Preparation of Zr modified Ni2P/SBA-15 catalysts and its hydrodeoxygenation performance

Ni₂P/ZrO₂-SBA-15(n) and Ni₂P/ZrO₂-SBA-15(m) catalysts were prepared from n-propoxide zirconium (n) and Zr(SO₄)₂(m) as zirconium sources. The catalysts were characterized by X-ray diffraction (XRD), N₂ adsorption specific surface area measurements (BET), CO uptake, X-ray photoelectron spectroscopy (XPS) and NH₃ temperature programmed desorption (NH₃-TPD). The results show that after Zr modification, a new layered structure of ZrP is formed. The introduction of Zr helps to generate more Ni₂P active phase with smaller crystal size, and increase both the acid strength and acid amount of the catalyst. Compared with zirconium n-propoxide, the catalyst prepared from Zr(SO₄)₂ has larger specific surface area, more acid amount, stronger acidity, more ZrP phases, smaller Ni₂P crystal grains and more Ni active sites. The product yields of benzofuran hydrodeoxygenation (BF HDO) given by Ni₂P/ZrO₂-SBA-15(n) and Ni₂P/ZrO₂-SBA-15(m) were 71.5% and 85.9% respectively, which were increased by 14.0% and 28.4% respectively compared with Ni₂P/SBA-15. The BF HDO activity, selectivity and yield of the BF HDO products decreased in the order of Ni₂P/ZrO₂-SBA-15(m) > Ni₂P/ZrO₂-SBA-15(n) > Ni₂P/SBA-15.